JPH06194774A - Silver halide photographic material and image forming method using it - Google Patents

Abstract

PURPOSE:To provide contrasty photographic property with a gamma exceeding 10 by use of a stable developer by providing a silver halide emulsion consisting of specified silver halide particles, containing a hydrazine derivative in the emulsifier layer, and spectrally sensitizing the silver halide emulsifier by a specified pigment. CONSTITUTION:A silver halide emulsion is formed of chemically sensitized silver halide particles with 50 mole % or more of silver chloride content which contains 1X10<-8>-5X10<-6>, per mole of silver, of a rhodium compound and 1X10<-8>-1X10<-6> mole of an iridium compound, and a hydrazine derivative is contained in one layer of the emulsifier layer or other hydrophilic colloidal layers. The silver halide emulsion is spectrally sensitized by a specified pigment. In the formula, Z and Z1 each represent a nonmetallic atomic group necessary for nitrogenous heterocyclic nucleus, R and R1 each represent an alkyl group, Q and Q1 each represent a nonmetallic atomic group necessary for 4- tiazolidinone nucleus. L and L1 each represent a methine group, X represents an anion, and n1, n2 and m each represent 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a superhigh-contrast silver halide photographic light-sensitive material suitable for a scanner and an image setter using a He-Ne laser as a light source.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system showing photographic characteristics of ultra-high contrast (especially γ of 10 or more) in order to favorably reproduce a continuous tone image or a line image by a halftone image. is necessary.
There is a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics. One of them is US Pat. Nos. 4,166,742 and 4,16.
8,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added to a sulphite preservative.
A system has been proposed which forms a super-high contrast negative image in which γ exceeds 10 by processing with a developer having a pH of 11.0 to 12.3 containing 5 mol / liter or more. This new image forming system can only use silver chlorobromide, which has a high content of silver chloride in conventional ultrahigh contrast image formation, whereas silver iodobromide and silver chloroiodobromide can also be used. There is. Another feature is that the conventional lith developer can contain a very small amount of sulfite preservative, whereas it can contain a large amount of sulfite preservative, so that it has relatively good storage stability. . However, a developer having a pH of 11 or more is easily oxidized by air and is unstable, and cannot be stored or used for a long time. Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 A processing method of developing with a developing solution of 0.0 or less is described. However, the emulsions used in these inventions are silver bromide and silver iodobromide emulsions, and their photographic performance changes greatly with development progress or compositional changes of processing solutions, and are not sufficient in terms of stability. I can't say.

US Pat. Nos. 4,998,604, 4,
994, 365 and 4,975,354 disclose a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, from the description of the examples, these inventions do not have sufficient contrast, and it is difficult to obtain the contrast and required Dmax under practical development processing conditions. Further, the nucleating hard contrast material using a hydrazine derivative has a wide range of change in photographic property with a change in pH of the developer. The pH of the developer greatly changes due to air oxidation of the developer and increase due to concentration by evaporation of water, or decrease due to absorption of carbon dioxide in the air. Therefore, attempts have been made to reduce the dependence of photographic performance on the pH of the developer.

An example using chemically sensitized silver chlorobromide in a system using hydrazines is disclosed in JP-A-53-20921,
60-83028, 60-140399, 6
3-46437, 63-103230, JP-A-3
-294844, 3-294845, 4-17
No. 4424 and Japanese Patent Application No. 3-188230. On the other hand, an example in which a silver halide emulsion containing a heavy metal complex such as hydrazine and rhodium or iridium is used in combination is
JP-A-60-83028, 61-47942, 61-47943, 61-29837, and 62-.
201233, 62-235947, 63-1
No. 03232 and the like. An example containing a cyanine dye having an anion charge in a system using hydrazines is an alkali salt of 5,5′-dichloro-9-ethyl-3,3′-bis (3-sulfopropyl) oxacarbocyanine. A number of them have been disclosed at the beginning, and examples thereof include JP-A-61-29837 and 62-235947.
No. 62-280733, No. 62-280734.
No. 2, JP-A No. 2-40, No. 2-124560, No. 2-
No. 262653, No. 3-63641 and the like.

On the other hand, as a hydrazine-containing photosensitive material for He-Ne laser use, Japanese Patent Application Laid-Open No. 4-17864 has been proposed.
No. 4, JP-A-4-275541 and the like,
In particular, JP-A-4-275541 describes a method of processing with a developer having a pH of 11 or less, but photographic performance changes due to fatigue of the developer, and it is still unsatisfactory in terms of stability. It was

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to:
An object of the present invention is to provide a silver halide photographic light-sensitive material for He-Ne lasers which can obtain extremely hard photographic properties with a gamma of more than 10 using a stable developer. A second object of the present invention is to obtain a high contrast with a developing solution having a pH of 11 or less so that the performance variation is small even when a large amount of a film is processed, and the performance variation is small even if the film is processed with a developing solution with advanced air oxidation, and a black spot is generated. The object is to provide a silver halide photographic light-sensitive material for He-Ne laser, which is less likely to generate.

[0007]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion is 1 × 10 ⁻ per mol of silver. ⁸ to 5 × 10 ^-6 mol of rhodium compound and / or 1 × 10 ^-8 to 1 × per mol of silver
It comprises chemically sensitized silver halide grains having a silver chloride content of 50 mol% or more containing 10 ^-6 mol of an iridium compound, The silver halide emulsion containing a hydrazine derivative has the following general formula [1],
It is achieved by a silver halide photographic light-sensitive material characterized by being spectrally sensitized with at least one dye selected from [2] and a dye of the general formula [X]. General formula [1]

[0008]

[Chemical 7]

In the formula, Z and Z ₁ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R and R ₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together are 4-thiazolidinone, 5-thiazolidinone or 4
Represents a group of non-metallic atoms necessary to complete the imidazolidinone nucleus. L, L ₁ and L ₂ each represent a methine group or a substituted methine group. n ₁ and n ₂ each represent 0 or 1. X represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt. General formula [2]

[0010]

[Chemical 8]

[Wherein Y ₁ and Y ₂ are each a non-metal necessary for forming a heterocycle such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring] It represents an atomic group, and these heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R ₁ and R ₂ each represent a lower alkyl group, an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R ₃ represents a methyl group, an ethyl group or a propyl group. X ₁ represents an anion. n ₁ and n ₂ represent 1 or 2. m represents 1 or 0, and in the case of an inner salt, m = 0. ] General formula [X]

[0012]

[Chemical 9]

Z ₁ and Z ₂ are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus and selenazoline nucleus, respectively. , A pyridine nucleus, a benzimidazole nucleus, or a quinoline nucleus represents a group of nonmetallic atoms necessary for completing the nucleus. R ₁ and R ₂ each represent an alkyl group or an aralkyl group, at least one of which has an acid group. X is a charge balance counterion, m
Represents 0 or 1.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide or silver iodochlorobromide having a silver chloride content of 50 mol% or more. The silver iodide content is 3 mol% or less, more preferably 0.
It is 5 mol% or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is 0.
It is preferably 1 μm to 0.7 μm, more preferably 0.
It is 2 μm to 0.5 μm. Regarding particle size distribution,
It is preferable that the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less and the particle size distribution is narrow. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is described in P.
Chimie et Physique Photographique by Glafkides (P
aul Montel, 1967), GF Dufin, Photogra
phic Emulsion Chemistry (The Forcal Press, 19
66), by VL Zelikman et al Making nd Coating P
hotographic Emulsion (The Focal Press, 1964
, Etc.) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide photographic light-sensitive material of the present invention preferably contains a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaammine rhodium ( Examples thereof include III) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg KCl, NaCl, KBr, Na
A method of adding Br or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound according to the present invention is 1 × per mol of finally formed silver halide.
10 ^{-8 to} 5 × 10 ^-6 mol is suitable, preferably 5 ×
It is 10 ⁻⁸ to 1 × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Although various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which is previously doped with iridium when preparing the silver halide.

The total addition amount of the iridium compound according to the present invention is 1 per mol of the finally formed silver halide.
^{X10 -8 to} 5 X 10 ^-6 mol is suitable, and preferably 5
It is x10 ^-8 to 1 x 19 ^-6 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is preferably chemically sensitized, and sulfur sensitization, selenium sensitization, tellurium sensitization,
Known methods such as reduction sensitization and gold sensitization can be used, and they can be used alone or in combination.

The sulfur sensitizer used in the present invention includes
In addition to the sulfur compound contained in gelatin, various sulfur compounds, such as thiosulfates, thioureas, thiazoles, rhodanins, etc., can be used. Specific examples are U.S. Pat. Nos. 1,574,944 and 2,278,947.
No. 2, ibid. 2,410,689, ibid. 2,728,668
Nos. 3,501,313 and 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3.
The range is from 8.0 to 8.0. In addition, Moisar, Klein Gelatin
The method of combining polyvinylpyrrolidone and thiosulfate as reported by e.Proc.Syme.2nd, 301-309 (1970) et al. also gives good results. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are US Pat. No. 2,448,060,
It is described in British Patent No. 618,061 and the like. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. To those skilled in the art, when it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

The tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320.
069, 3,772,031, British Patent No. 23
No. 5,211, No. 1,121,496, No. 1,29
5,462, 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Chem.
Soc. Chem. Commun.) 635 (1980), ibid 11
02 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Trans (J. Chem. Soc. Perkin Trans.) 1,
It is preferable to use the compounds described in 2191 (1980) and the like. Specific tellurium sensitizers include colloidal tellurium and telluroureas (eg, allyl tellurourea, N,
N-dimethyl tellurourea, tetramethyl tellurourea, N
-Carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'
-Diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide,
N, N-dimethyl tellurobenzamide), tellurohydrazide (eg N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg t-butyl-t)
-Hexyl telluroester), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (eg United Kingdom Examples thereof include negatively charged telluride ion-containing gelatin described in Japanese Patent No. 1,295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, and allyl tellurocyanate).

Next, the sensitizing dye of the general formula [1] used in the present invention will be described. As the nitrogen-containing heterocyclic nucleus completed by Z or Z ₁ , the following can be used.
Thiazole nucleus {eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-di-phenylthiazole etc.}, benzothiazole nucleus {eg benzothiazole, 5-chlorobenzothiazole, 6- Chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5- Ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-carboxybenzothiazole, 5-fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-acetylaminobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethyl Benzothiazole, 5-hydroxy-6-methylbenzothiazole, 5,6-dimethoxybenzothiazole, tetrahydrobenzothiazole, etc.}, naphthothiazole nucleus {eg naphtho [2,1 d] thiazole, naphtho [1,2
-D] thiazole, naphtho [2,3-d] thiazole,
5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] Thiazole etc., selenazole nucleus {eg 4-methylselenazole, 4-phenylselenazole etc.), benzoselenazole nucleus {eg benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-methoxybenzo Selenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.}, naphthoselenazoles {for example, naphtho [2,1-d] selenazole, naphtho [1,2]
-D] selenazole etc.}, oxazole nucleus {eg oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole etc.), benzoxazole nucleus {eg benzoxazole, 5-fluorobenzoxazole, 5-chlorobenz Oxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6- Dimethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-acetylbenzoxazole,
5-hydroxybenzoxazole, etc., naphthoxazole nucleus {eg, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,
3-d] oxazole and the like}, 2-quinoline nucleus, imidazole nucleus, benzimidazole nucleus, 3,3'-dialkylindolenine nucleus, 2-pyridine nucleus, thiazoline nucleus and the like can be used. Particularly preferably Z and Z
_At least one of 1 is a thiazole nucleus, a benzothiazole nucleus, a thiazoline nucleus, an oxazole nucleus or a benzoxazole nucleus.

As the alkyl group represented by R or R ₁ in the above general formula, an alkyl group having 5 or less carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), substituted As the alkyl group, a substituted alkyl group having 5 or less carbon atoms in the alkyl radical (for example, hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, etc.), carboxyalkyl group (for example, carboxymethyl group) Group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2- (2-carboxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group) , 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2- 3-sulfopropoxy) ethyl group,
2-acetoxy-3-sulfopropyl group, 3-methoxy-2- (3-sulfopropoxy) propyl group, 2- [3
-Sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3- (3'-sulfopropoxy) propyl group, etc.), aralkyl group (the number of carbon atoms of the alkyl radical is 1 to
5 is preferable, and the aryl group is preferably a phenyl group, for example, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, p-tolylpropyl group, p-
Methoxyphenethyl group, p-chlorphenethyl group, p-
Carboxybenzyl group, p-sulfophenethyl group, p-
Sulfobenzyl group, etc., aryloxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, aryl group of aryloxy group is preferably phenyl group, for example, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, p -Methylphenoxyethyl group, p-
Methoxyphenoxypropyl group, etc.), vinylmethyl group, etc.}, etc., and an aryl group such as a phenyl group. L, L ₁ and L ₂ are methine groups or substituted methine groups =
Represents C (R ')-. R'is an alkyl group (such as a methyl group or an ethyl group), a substituted alkyl group (such as an alkoxyalkyl group (such as a 2-ethoxyethyl group)),
Carboxyalkyl group (for example, 2-carboxyethyl group), alkoxycarbonylalkyl group (for example, 2-carboxyethyl group)
Methoxycarbonylethyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), etc.}, aryl group (eg phenyl group, p-methoxyphenyl group, p
-Chlorophenyl group, o-carboxyphenyl group, etc.)
And so on. Further, L and R, and L ₁ and R ₁ may be bonded to each other by a methine chain to form a nitrogen-containing heterocycle. Q
Examples of the substituent attached to the nitrogen atom at the 3-position of the thiazolinone nucleus or the imidazolinone nucleus formed by Q and Q ₁ include an alkyl group (preferably having a carbon number of 1 to 8 such as a methyl group, an ethyl group, a propyl group). , Allyl group, aralkyl group (alkyl group, radical preferably has 1 to 5 carbon atoms, for example, benzyl group, p-carboxyphenylmethyl group, etc.), aryl group (total carbon number is preferably 6 to 9, eg phenyl group) , P-carboxyphenyl group, etc., a hydroxyalkyl group (the carbon number of the alkyl radical is preferably 1 to 5, for example, a 2-hydroxyethyl group), a carboxyalkyl group (the carbon number of the alkyl radical is preferably 1 to 5, For example, carboxymethyl group, etc., alkoxycarbonylalkyl group (alkyl radical of alkoxy part) Preferably 1 to 3 carbon atoms, also the number of carbon atoms in the alkyl moiety preferably 1 to 5, for example, a methoxycarbonylethyl group) and the like.

Examples of the anion represented by X are halogen ion (iodine ion, bromine ion, chlorine ion, etc.), perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, Examples thereof include methylsulfate ion and ethylsulfate ion. Next, specific compound examples will be given.

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

[Chemical 14]

[0033]

[Chemical 15]

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

Next, the sensitizing dye represented by the general formula [2] will be described. Examples of the lower alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group and a butyl group, and examples of the alkyl group having a sulfo group include a β-sulfoethyl group and a γ-sulfopropyl group. , Γ-sulfobutyl group, δ-sulfobutyl group, sulfoethoxyethyl group, sulfopropoxyethyl group and the like.
Examples of the lower alkyl group represented by R ₃ include a methyl group, an ethyl group and a propyl group. A and B each represent a nonmetal atom group necessary for completing a naphthothiazole ring, a benzothiazole ring, a naphthoselenazole ring or a benzoselenazole ring, and each of these rings has a lower alkyl group (eg ethyl group). Group, methyl group, etc.), alkoxy group (eg methoxy group, ethoxy group etc.), hydroxyl group, aryl group (eg phenyl group), alkoxycarbonyl group (eg methoxycarbonyl group), halogen atom (eg chlorine atom, bromine atom etc.) ) Etc. are included. The lower alkyl group includes a case where it is substituted. Examples of the naphthothiazole ring, the benzothiazole ring, the naphthoselenazole ring, and the benzoselenazole ring completed by the nonmetallic atom group substituting these substituents are [1,2-d] and [2,3-d]. , And [2,1-
d] naphthothiazole, benzothiazole, 5-methylbenzothiazole, 5-chlorobenzothiazole, 5-
Methoxybenzothiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, 5-cyanobenzothiazole, 5-phenylbenzothiazole, 5-
Hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-ethoxy-6-ethylbenzothiazole, 5-ethoxy-6-butylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5
-Carboxybenzothiazole, [1,2-d],
[2,3-d] and [2,1-d] naphthoselenazole, benzoselenazole, 5-methylbenzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselena Zol,
Examples thereof include 5,6-dimethylbenzoselenazole and 5-hydroxybenzoselenazole.

X ⁻ represents an anion usually used for cyanine dyes, for example, a halogen ion, a benzenesulfonate ion, a p-toluenesulfonate ion and the like. m represents 1 or 0, and when R ₁ or R ₂ forms an inner salt, m represents 0. Specific examples of the sensitizing dye represented by the general formula [2] include, for example, Japanese Patent Application No. 2-14430, page 9,
The sensitizing dyes shown in Nos. 1 to 30 on page 14 are preferably used. The representative examples are listed below.

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

The compound represented by the general formula [X] will be described. The alkyl groups represented by R ₁ and R ₂ include unsubstituted and substituted alkyl groups, at least one of which has an acid group such as a sulfo group or a carboxyl group. The unsubstituted alkyl group preferably has 18 or less, particularly 8 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group and an n-octadecyl group. To be Further, the substituted alkyl group preferably has 6 or less carbon atoms in the alkyl portion, particularly preferably 4 or less carbon atoms. For example, an alkyl group substituted with a sulfo group (a sulfo group is They may be bonded via an alkoxy group, an aryl group, etc. For example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
(3-sulfopropoxy) ethyl group, 2- [2- (3-
Sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, p-sulfophenethyl group,
Alkyl group substituted with a carboxy group such as p-sulfophenylpropyl group (the carboxy group may be bonded via an alkoxy group, an aryl group, etc.), for example, carboxymethyl group, 2-carboxyethyl group, 3- Carboxypropyl group, 4-carboxybutyl group, etc.), hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.), acyloxyalkyl group (eg, 2-acetoxyethyl group, 3-acetoxy) Propyl group), alkoxyalkyl group (eg 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (eg 2-
Methoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), vinyl group-substituted alkyl group (eg, allyl group), cyanoalkyl group (eg, 2-cyanoethyl group), carbamoylalkyl group (eg, 2-carbamoylethyl group, etc.), aryloxyalkyl group (eg, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.), aralkyl group (eg, 2-phenethyl group, 3-phenylpropyl group, etc.), or aryloxyalkyl group. (Eg 2
-Phenoxyethyl group, 3-phenoxypropyl group, etc.) and the like.

The charge-balance counterion X is any anion capable of canceling the positive charge generated by the quaternary ammonium salt in the heterocycle, for example, bromide ion, chloride ion, iodine ion, p-toluene. Examples thereof include sulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, and thiocyanate ion. In this case, n is 1. Charge balance counter ion X
If either R ₁ or R ₂ contains an anionic substituent such as a sulfoalkyl substituent, the salt can be in the form of betaine, in which case no counterion is required and m Is 0. When R ₁ and R ₂ have two anionic substituents, for example two sulfoalkyl groups, X is a cationic counterion, such as an alkali metal ion (sodium ion, potassium ion, etc.) or Examples thereof include ammonium salts (triethylammonium, etc.).

The compound represented by the general formula [X] preferably has substantially no absorption maximum in the visible light region. Here, the compound "having substantially no absorption maximum in the visible light region" means a compound having a color tone of a level below which a residual color on a photographic light-sensitive material is practically no problem, and more specifically, a development treatment. The residual color after that is a compound having a color tone below a level at which there is no practical problem. The absorption maximum of the above compound in methanol is preferably 460 nm or less, more preferably 430 nm or less. Specific examples of the compound represented by the general formula [3] are shown below.

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

[0051]

[Chemical 28]

[0052]

[Chemical 29]

[0053]

[Chemical 30]

General formulas [1], [2], and
To incorporate the spectral sensitizing dye represented by the formula [X] into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, Methyl cellosolve, 2,2
3,3, -Tetrafluoropropanol, 2,2,2-
Trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-
It may be added to the emulsion by dissolving it in a solvent such as 2-propanol or N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24,185 and the like, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion, JP-B-44-23. , 389, Japanese Patent Publication No. 44-2
No. 7,555, Japanese Patent Publication No. 57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an aqueous solution is prepared by coexisting an acid or a base into the emulsion. Method of adding, as described in U.S. Pat. No. 3,822,135 and U.S. Pat. No. 4,006,025, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion. , JP-A-53-10
No. 2,733 and JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-74,6.
As described in No. 24, it is also possible to use a method in which a dye is dissolved using a compound that causes red shift and the solution is added to an emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been recognized to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, and the like, as disclosed in the specification of the silver halide grain formation step or / and before desalting, during the desalting step and / or desalting step. From the time after salting to before the start of chemical aging, JP-A-58-1
As disclosed in the specification of No. 13,920, etc., it may be added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated until after the chemical ripening and before the coating. May be. US Pat. No. 4,225,6
66, JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure, for example, during the grain forming step and the chemical ripening step. Alternatively, it may be added in divided portions such as after completion of chemical aging or before or after chemical aging or after completion of the step, and the type of compound or combination of compounds added in division may be changed. May be added.

The general formulas [1], [2], and
The addition amount of the spectral sensitizing dye represented by [X] varies depending on the shape and size of the silver halide grains, but is 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. be able to. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain, The addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The hydrazine derivative used in the present invention is
The compounds represented by the general formulas [3] to [5] are preferable.

First, the hydrazine derivative of the general formula [3] will be described. General formula [3]

[0059]

[Chemical 31]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent, —O— (CH ₂ CH _{2
2 O) n -, - O-} (CH 2 CH (CH 3) O) n - or _{-O- (CH 2 CH (OH)} CH 2 O) n - moiety of (where n is an integer of 3 or more) Or a group containing a quaternary ammonium cation as a part of the substituent. G ₁ is a -CO- group, a -COCO- group,-
CS- _{group, -C (= NG 2 R 2} ) - group, -SO- group, -
It represents a SO ₂ — group or a —P (O) (G ₂ R ₂ ) — group.
G ₂ is a simple bond, -O- group, -S- group or -N
(R ₂ )-group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, the other is a hydrogen atom or an acyl group,
Represents an alkyl or aryl sulfonyl group.

General formula [3] will be described in more detail. In the general formula [3], the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
This alkyl group has a substituent. In the general formula [3], the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. Chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 carbon atoms)
To 30), an alkoxy group (preferably having a carbon number of 1 to 1)
30), substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 carbon atom). And a phosphoric acid amide group (preferably having 1 to 40 carbon atoms).

The aliphatic group, aromatic group or their substituents for R ₁ is --O-(CH ₂ CH ₂ O) _n- , --O-(CH
_{2 CH (CH 3) O)} n - or -O- (CH ₂ CH
Contains (OH) CH ₂ O) _n − or 4
It contains a quaternary ammonium cation. n is an integer of 3 or more, preferably an integer of 3 or more and 15 or less. R ₁ is preferably represented by the following general formula [H1], general formula [H2], general formula [H3] or general formula [H4].

[0064]

[Chemical 32]

In the formula, L ₁ and L ₂ are --CONR ₇ --groups,
NR ₇ CONR ₈ — group, —SO ₂ NR ₇ — group or —N
And R ₇ SO ₃ NR ₈ — groups, which may be the same or different. R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. m is 0 or 1. R ₃ , R ₄ and R ₅ are divalent aliphatic groups or aromatic groups, preferably alkylene groups, arylene groups or their groups and —O— groups, —CO— groups, —S— groups, —SO—.
Group, -SO ₂ - group, -NR ₉ - group (R ₉ of the general formula (2), (3), R ₇ as defined in (4)) is a divalent group produced by combining a. More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or a divalent group formed by combining them with an —S— group, —SO— group or —SO ₂ — group, and R ₄ , R ₅ Has 6 to 2 carbon atoms
It is an arylene group of 0. Particularly, R ₅ is preferably a phenylene group. R ₃ , R ₄ and R ₅ may be substituted, and preferable substituents include those listed as the substituents for R ₁ .

In formulas [H1] and [H2], Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Z
Preferred examples of the nitrogen-containing heteroaromatic ring formed by ¹ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring,
Examples thereof include a pyrazine ring, an imidazole ring, a pyrazole ring, a pyrrole ring, an oxazole ring, a thiazole ring, and a benzo-condensed ring thereof, as well as a pteridine ring and a naphthyridine ring. General formula [H2], [H3], [H
In 4], X ⁻ represents a counter anion moiety when forming a counter anion or an inner salt. General formula [H2],
In [H3] and [H4], R ⁶ represents an aliphatic group or an aromatic group. R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. General formula [H
The three R ₆ in 3] may be the same or different, and may combine with each other to form a ring.
Z ₁ and R ₆ may be substituted, and preferable substituents include those listed as the substituents for R ₁ . In the general formula [H4], L ₃ is —CH ₂ CH ₂ O—.
_{Group, -CH 2 CH (CH 3)} O- group, or -CH ₂ C,
Represents H (OH) CH ₂ O- groups, n represents the same meaning as in formula [H1].

G ₁ in the general formula [3] is --CO
- group, -SO ₂ - groups are preferred, -CO- group is most preferred. A hydrogen atom is preferable as A ₁ and A ₂ .

The alkyl group represented by R ₂ in the general formula [3] is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). Including rings). When G ₁ is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, methoxymethyl group, phenoxymethyl group, trifluoromethyl group, 3-hydroxy group). Propyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-
Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc., and a hydrogen atom is particularly preferable. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. Also, R
₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the —R ₂ portion, and examples thereof include those described in JP-A-63-29751.

R ₁ or R _{2 in} the general formula [3] may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-1005
Those described in No. 30 are mentioned.

R ₁ or R _{2 in} the general formula [3] may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
4,459,347, JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned.

The compounds of the general formula [3] of the present invention are disclosed in, for example, JP-A Nos. 61-213,847 and 62-260,153.
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-8
03, U.S. Pat. Nos. 3,379,529 and 3,62.
0,746, 4,377,634, 4,33
2,878, JP-A-49-129,536 and 56.
-153,336, 56-153,342, U.S. Pat. Nos. 4,988,604, 4,994,365 and the like can be used for the synthesis. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0072]

[Chemical 33]

[0073]

[Chemical 34]

Next, the compound represented by the general formula [4] will be described in more detail. General formula [4]

[0075]

[Chemical 35]

R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted. G ¹ is -CO-
Group, -SO ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or -P (O) (R
₃ )-group, and R ₂ represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group. R ₃ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group.

Next, the compound represented by the general formula [4] will be described in more detail. In the general formula [4], R
_The aliphatic group represented by ₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. R ₁
The aromatic group represented by is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R ₁ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, a benzthiazolyl group. Those are preferable. R
Preferred as ₁ are aromatic groups, nitrogen-containing heterocycles and groups represented by general formula (b). General formula (b)

[0078]

[Chemical 36]

(In the formula, X _b represents an aromatic group or a nitrogen-containing heterocyclic group, R _b ^{1 to} R _b ⁴ each represent a hydrogen atom, a halogen atom, or an alkyl group, and X _b and R _b ¹
R _b ⁴ may have a substituent if possible.
r and s represent 0 or 1. ) R ₁ is more preferably an aromatic group, and particularly preferably an aryl group.
R ₁ may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Group, hydroxy group, halogen atom,
In addition to cyano group, sulfo group, carboxyl group, alkyl and aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, nitro group, alkylthio group, arylthio group, the following general formula The group represented by (c) may be mentioned. General formula (c)

[0080]

[Chemical 37]

In the formula (c), Yc is --CO-- or --SO.
_{2 -, - P (O)} (R C3) - (. Wherein, R _C3 alkoxy group or an aryloxy group) or -O
Represents P (O) ( _RC3 )-, L is a single bond, -O-,-
S- or -NR _C4- (in the formula, R _C4 represents a hydrogen atom, an alkyl group or an aryl group). R _C1 and R
_C2 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and may be the same or different, or may be bonded to each other to form a ring. R ₁ may include one or more of general formula (c).

In the general formula (c), the aliphatic group represented by R _C1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocycle of R _C1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R _C1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , Halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group. When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _C2 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C2 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C2 may be substituted with a substituent. Examples of the substituent include those listed as R _C1 in the general formula (c) and the substituent. If possible, R _C1 and R _C2 may be linked to each other to form a ring. A hydrogen atom is more preferable as R _C2 .

Y _C in the general formula (c) is -CO.
-, - SO ₂ - is particularly preferred, L is a single bond and -N
R _C4 − is preferred. The aliphatic group represented by R _C4 in the general formula (c) is a linear, branched or cyclic alkyl group,
It is an alkenyl group or an alkynyl group. The aromatic group represented by R _C4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C4 may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R _C1 in the general formula (c). A hydrogen atom is more preferable as R _C4 .

Most preferably, G in general formula [4] is a -CO- group. R _{2 in the} general formula [4] represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, and preferably two electron withdrawing groups,
Particularly preferred is a substituted alkyl group substituted with three electron withdrawing groups.

The electron-withdrawing group for substituting the carbon atom substituted with G of R ₂ preferably has a δ _p value of 0.2 or more and a δ _m value of 0.3 or more, for example, halogen, cyano, nitro, Nitroso, polyhaloalkyl, polyhaloaryl,
An alkyl or aryl carbonyl group, a formyl group,
Alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate group, phosphon It represents an acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, and an electron-deficient heterocyclic group. R _{2 in the} general formula [4] particularly preferably represents a trifluoromethyl group.

R ₁ and R _{2 in} the general formula [4] may be those in which a ballast group or a polymer commonly used in a non-moving photographic additive such as a coupler is incorporated. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-100530
The items described in No.

R ₁ and R _{2 in} the general formula [4] may be those in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, which are disclosed in U.S. Pat. Nos. 4,385,108, 4,459,347, and JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0089]

[Chemical 38]

[0090]

[Chemical Formula 39]

Next, the compound of the general formula [5] will be described in detail.

[0092]

[Chemical 40]

In the general formula [5], the aliphatic group represented by R _a is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by _Ra is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R _a is a negative saturated or unsaturated hetero ring of 3 to 10 containing at least one of N, O, or S atoms, which may be a single ring or other A condensed ring may be formed with the aromatic ring or the hetero ring of. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and examples thereof include a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzthiazolyl group. preferable.

R _a may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group. Group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group. When possible, these groups may be linked to each other to form a ring. Preferred as R _a is
An aromatic group, more preferably an aryl group.

Preferred among the groups represented by R _b are:
When G ₁ is a carbonyl group, a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group) Etc.), an aryl group (for example, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, etc.) and the like, and a hydrogen atom is particularly preferable. When G ₁ is a sulfonyl group, R _b is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxyphenylmethyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, Dimethylamino group) and the like are preferable.

When G ₁ is a sulfoxy group, preferred R _b
Is a cyanobenzyl group, a methylthiobenzyl group or the like, and when G ₁ is a phosphoryl group, R _b is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group. G ₁
When is an N-substituted or unsubstituted iminomethylene group, preferred R _b is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent of R _b , the non-substituted groups listed for R _a can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group or a nitro group can be applied. These substituents may be further substituted with these substituents. If possible, these groups may form a ring in which these groups are connected to each other. R _a or R _b
Adsorption-promoting groups on silver halide which can be substituted with X _1- (L
₁ ) It can be represented by _q −. Here, X ₁ is an adsorption promoting group to silver halide, and L ₁ is a divalent linking group.
q is 0 or 1.

Preferred examples of the adsorption accelerating group for silver halide represented by X ₁ include a thioamide group, a mercapto group, a group having a disulphide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption-promoting group represented by X ₁ is a divalent group represented by —CS-amino-, which may be a part of the ring structure or an acyclic thioamide group. . Useful thioamide adsorption-promoting groups include, for example, U.S. Pat. Nos. 4,030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, and US Pat. No. 4,266,013, and No. 4,276,364,
And "Research Disclosure" (Research
Disclosure) Volume 151 No. 15162 (November 1976) and Volume 176 No. 17626 (1978).
You can choose from those disclosed in (December, 2012).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione and 4-thiazoline-2-thione group. Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like can be mentioned. It may be substituted. The mercapto group of X ₁ is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship therewith Synonymous with the group, and specific examples of this group are the same as those listed above).

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by X ₁ include 5- or 6-membered nitrogen-containing heterocyclic ring composed of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of R _a can be mentioned. Among those represented by X ₁ , preferred ones are the present thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles, such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole. Group, 2-mercapto-
1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.).

Two or more X _1- (L ₁ ) _q groups may be substituted and may be the same or different. The divalent linking group represented by L ₁ is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group,
Arylene group, -O-, -S-, -NH-, -N =,-
CO—, —SO ₂ — (these groups may have a substituent), etc., or a combination thereof. These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of R _a can be mentioned.

A ₁ and A ₂ are substituted with a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or Hammett's substituent constant sum of -0.5 or more). Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's substituent constants is −).
A benzoyl group substituted to have a concentration of 0.5 or more, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (eg, a substituent is a halogen atom, an ether group, a sulfonamide group, or a carbonamido group). , Hydroxyl group,
Examples thereof include a carboxy group and a sulfonic acid group. ), And
The sulfinic acid residues represented by A ₁ and A ₂ are specifically those described in US Pat. No. 4,478,928. A hydrogen atom is most preferable as A ₁ and A ₂ . A carbonyl group is most preferable as G _{1 in the} general formula [5]. Among those represented by the general formula [5], preferred ones can be represented by the general formula [5-a]. General formula [5-
a]

[0102]

[Chemical 41]

[0103] In the formula, R _'a are those from R _a in formula (5) by removing one hydrogen atom. Here, at least one of R ′ _a , R _{b and} L ₁ has a group capable of dissociating into an anion having a pKa of 6 or more or an amino group. pKa6
Among the groups capable of dissociating into the above anions, the preferable ones are substituents capable of dissociating into anions of pKa8 to 13, which hardly dissociate in a neutral or weakly acidic medium (alkaline aqueous solution such as a developer). Preferably pH 10.5-1
It does not have to be a specific one as long as it can be sufficiently dissociated in 2.3).

For example, a hydroxyl group, a group represented by --SO ₂ NH--, a hydroxyimino group, an active methylene group, or an active methine group (for example, --CH ₂ COO--, --CH ₂ CO--,
-CH (CN) -COO- and the like).
The amino group may be primary, secondary, or tertiary, and the conjugate acid preferably has a pKa of 6.0 or more. A ₁ , A ₂ , G ₁ , R _b , L ₁ , X ₁ and q
Has the same meaning as described in the general formula [5]. Among those represented by the general formula [5], particularly preferable ones are those represented by the general formula [5-b]. General formula [5-b]

[0105]

[Chemical 42]

In the formula, L ₂ has the same meaning as L ₁ in the general formula [5] and the general formula [5-a], and Y ₁ has the same meaning as the substituent of R _{1 in} the general formula [5]. And q represents 0 or 1, 1 represents 0, 1, or 2, and when 1 is 2, Y may be the same or different. A ₁ , A ₂ , G ₁ , R _b ,
L ₁ and X ₁ have the same meanings as described in the general formulas [5] and [5-a]. Furthermore, preferably X _1- (L ₂ ) _q
—SO ₂ NH is a hydrazino group substituted at the p-position. The compound of the general formula [5] is disclosed in JP-A-56-678.
43, ibid. 60-179734, Japanese Patent Application No. 60-7818.
2. Japanese Patent Application No. 60-111936, Japanese Patent Application No. 61-1150
36, etc. according to the method described in. Specific examples of the compound represented by the general formula [5] are shown below. However, the present invention is not limited to the following compounds.

[0107]

[Chemical 43]

[0108]

[Chemical 44]

The addition amount of the hydrazine compound in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 1 mol per mol of silver halide.
0 ^-5 mol to 2 × 10 ^-2 mol per mol of silver is preferred. The hydrazine compound of the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformylamide, dimethylsulfoxide, and methyl cellosolve can be used by dissolving them. Also, by well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexane are dissolved to mechanically emulsify the dispersion. Can also be prepared and used. Alternatively, the hydrazine compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

In the present invention, an amino compound can be preferably used as the nucleation accelerator. Specific compounds include, for example, compounds represented by formulas (II-m) to (II-p) on page 9, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536. -1 to
II-22, the compounds described in JP-A-1-179939 and the general formula (I) described in Japanese Patent Application No. 4-237366.
Examples thereof include compounds of I), (III), (IV), (V) and (VI).
Specific examples of particularly preferable compounds are shown below, but the present invention is not limited to the following compounds.

[0111]

[Chemical formula 45]

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Various synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl butyral and the like can be used.

In order to obtain ultrahigh contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention has a sulfite ion as a preservative of 0.
A developer containing 15 mol / liter or more and having a pH of 9.6 to 11.0 can sufficiently obtain a super-high contrast negative image. There is no particular limitation on the developing agent used in the developer used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
There are 5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable. 1-phenyl-3-used in the present invention
As a developing agent for pyrazolidone or its derivative, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1- Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
Examples include -p-aminophenyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4,4-dimethyl-3-pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p
-When the combination with amino-phenols is used, the former is 0.05 mol / liter to 0.5 mol / liter,
It is preferable to use the latter in an amount of 0.06 mol / liter or less.

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.15 mol / liter or more, and particularly preferably 0.3 mol / liter or more. The upper limit is 2.
It is preferably up to 5 mol / liter. The alkaline agent used for setting the pH includes a pH adjusting agent and a buffering agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 9.6 and 11.0. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 5-
An indazole compound such as nitroindazole, an antifoggant such as 5-methylbenztriazole or a benztriazole compound such as a benztriazole compound or a black pepper inhibitor: may be contained, and if necessary, a toning agent and a surfactant. , Antifoaming agent, water softener, hardener, JP-A-56-10
The amino compound described in No. 6244 may be included.

The compounds described in JP-A-56-24,347 can be used in the developer of the present invention as a silver stain preventing agent. Japanese Patent Application No. Sho 6 as a dissolution aid added to the developer.
The compounds described in 0-109,743 can be used. Further, as a pH buffering agent used in a developing solution, Japanese Patent Laid-Open No.
No. 0-93,433 or Japanese Patent Application No.
The compounds described in -28708 can be used.
As the fixing agent, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light vane, etc.) as a hardening agent. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al / liter. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent. The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 43 ° C.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectroscopy described in JP-A Nos. 1-112235, 2-124560, 3-79928, and Japanese Patent Application Nos. 3-189532 and 3-411064. Sensitizing dye. 2) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to 4 Lower right column, line 18 3) Antifoggant JP-A-2-103536, JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538 Thiosulfinic acid compounds described in the public notice. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 6) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 8) Dyes Dyes in the lower right column, lines 1 to 18 of page 17 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 11) Redox compound A compound represented by the formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 13) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12 lower left column, and EP452772A.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0118]

【Example】

Example 1 An emulsion was prepared by the following method. Emulsion A: 0.13 M silver nitrate aqueous solution, and K ₂ Rh (H ₂ O) Cl corresponding to 1.5 × 10 ⁻⁷ mol per mol of silver
_An aqueous solution of halogen salt containing 0.04 M potassium bromide and 0.09 M sodium chloride containing ₅ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ was added to sodium chloride.
An average particle size of 0.14 was added to a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione by a double jet method at 38 ° C. for 12 minutes while stirring.
Nucleation was performed by obtaining silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 mol%. Then, similarly, 0.87M silver nitrate aqueous solution, 0.26M potassium bromide, and 0.65M
The aqueous solution of halogen salt containing sodium chloride of was added by the double jet method over 20 minutes. Emulsions A to D shown in Table 1 were prepared in the same manner.

Then, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method. Then
Further, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added per 1 mol of silver, and the mixture was heated at 60 ° C for 45 minutes for chemical sensitization and then stabilized. 4-hydroxy-6-methyl-1, as an agent
150 mg of 3,3a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains were cubic grains of silver iodochlorobromide having an average grain size of 0.25 μm and a silver chloride content of 69.9 mol%.
(Variation coefficient 10%)

Emulsion E A 0.13 M silver nitrate aqueous solution and 1.5 × per mol of silver
^Containing K ₂ Rh (H ₂ O) Cl ₅ corresponding to 10 ⁻⁷ mol and K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol,
An aqueous solution of a halogen salt containing 09M potassium bromide and 0.04M sodium chloride was added to sodium chloride and 1,3-
To obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 30 mol% by adding to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by a double jet method at 38 ° C. for 12 minutes while stirring. Nucleation was performed by. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a 0.61 M potassium bromide, and a 0.30 M sodium chloride-containing halogen salt aqueous solution were added over 20 minutes by the double jet method.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added for conversion, and the product was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver to prepare pH 6.5 and pAg 7.5, 60 ℃
The sensitizing dyes of the present invention and the following comparative compounds are shown in Table 2 below.
Was added as shown in. Further, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added per 1 mol of silver, and the mixture was heated at 60 ° C for 45 minutes for chemical sensitization and then stabilized. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (150 mg) was added as a preservative, and Proxel 100 was added as a preservative.
mg was added. The obtained particles have an average particle size of 0.25μ.
m, and silver iodochlorobromide cubic grains having a silver chloride content of 29.9 mol%. (Variation coefficient 10%)

Preparation of coating sample Add 2 × 10 ^-4 mol of the above-mentioned sensitizing dye 1-5 to 1 mol of silver in the obtained emulsion, and further add 4,4 as a supersensitizer.
75 mg of 4'-bis (4,6-naphthoxy-pyrimidin-2-ylamino) -stilbenedisulphonic acid disodium salt, 4 x 10 ^-4 mol of each of the compounds represented by the following (b) and (c), and a compound ( 3 × 10 ⁻⁴ mol of d),
2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline and 3 × 10 ⁻⁴ mol of the hydrazine derivative of Compound 3-1 were added per mol of silver. Furthermore, N-oleyl-
30 mg / m ^{2 of} N-methyltaurine sodium salt was added so that the water-soluble latex represented by (e) was 200 mg / m ² , and the nucleation accelerator represented by the following structural formula and polyethyl acrylate were dispersed. Of 200 mg / m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 8
8: 5: 7) 200 mg / m ² and 1, as a hardening agent
200 mg of 3-divinylsulfonyl-2-propanol
/ M ² was added. The pH of the solution was adjusted to 6.0. Coating them on a polyethylene terephthalate film consisting of a moistureproof layer undercoating containing vinylidene chloride on both sides with a silver amount of 3.0
It was applied so as to be g / m ² .

[0123]

[Chemical formula 46]

At this time, the sensitizing dye was added in an amount of 2 × 10 ^-4 mol per mol of silver as shown in Table 2. On these emulsion layers, as a protective layer, 1.0 g / m ² of gelatin and 40 mg / amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm
m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , sodium ethylthiosulfonate 5 mg
/ M ² , hydroquinone 200 mg / m ² , silicone oil 20 mg / m ^2, and 5 mg / m ^{2 of} fluorosurfactant represented by the following structural formula (f) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate. Then, the samples shown in Table 2 were prepared. The back layer and the back protective layer were applied by the following formulation.

[0125]

[Chemical 47]

[Back Layer] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 g / m ²

[0127]

[Chemical 48]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] dye [a] 50 mg / m ² Dye [b] 50 mg / m ² Dye [c] 150 mg / m ²

[0129]

[Chemical 49]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

[0131]

[Table 1]

The sample thus obtained was exposed to xenon flash light having an emission time of 10 ⁻⁵ seconds through an interference filter having a peak at 633 nm and a step wedge, and a developing solution having the following formulation was used as a developing solution and GR-F1 was used as a fixing solution.
(Manufactured by Fuji Photo Film Co., Ltd.), using FG-68
A 0A automatic processor (manufactured by Fuji Photo Film Co., Ltd.) was used to carry out processing at 35 ° C. and 30 ″. The evaluation results are shown in Table 2. Here, the sensitivity is 4.0 at a density of 35 ° C. and 30 ″ development.
The relative value of the reciprocal of the exposure dose giving γ is represented by the following formula

[0133]

[Equation 1]

It is defined by.

Further, the actual portion of the sample treated with the developing solution 4 was evaluated on a scale of 5 by observation with a microscope. "5" is the best and "1" is the worst. "5" and "4" are practical and "3"
Is poor but practically usable, and "2" or "1" is not practical. Developer 1 Replenisher 1,2-dihydroxybenzene-3,5-disulfonate sodium 0.5 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6.0 g Diethylene glycol 40.0 g 5-methylbenzotriazole 0.2 g hydroquinone 30.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2,3,5,6,7,8-hexahydro-2- Thioxo-4- (1H) -quinazolinone 0.09 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g Potassium hydroxide is added, water is added to 1 liter and the pH is adjusted to 10.7. 1 liter Starter Acetic acid (90%) 366 g Water was added to 1 liter To 1 liter of the replenisher, 10 ml of the starter was added to prepare Developer 1.

Developer 2 Concentrate Sodium metabisulfite 145 g Potassium hydroxide (45%) 178 g Diethylenetriamine pentaacetic acid pentasodium salt 15 g Sodium bromide 12 g Hydroquinone 65 g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.9 g Benzotriazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium hydroxide (50%) 46 g Boric acid 6.9 g Diethylene glycol 120 g Potassium carbonate (47%) 120 g Water 1 liter Concentrated liquid 1 Diluted with water to the ratio of 2 to pH 1
A developer 2 of 0.5 was made.

Developer 3 Developer 3 was prepared by using Developer 1 and running each sample (blackening rate 100%) after exposure in an amount corresponding to 30 sheets in total conversion without replenishment. Developer 4 Developer 1 was left unreplenished at 38 ° C. for 1 month without treating the sample to prepare Developer 4. Table 2 shows the results of treatment with the above four types of developers.

[0138]

[Table 2]

No. 1 and 2 to 6, No. 7 and 8, 9 No. 10
From the comparison between Nos. 11 and 12, the samples having the dye of the general formula [3] have a small difference in sensitivity between the developers 2, 3 and 4, and the black spots in the developer 4 are small, so that the developer is not fatigued. It is understood that the performance is stable. Also, No. 13-1
As shown in 6, it is understood that when an emulsion containing no iridium or rhodium or an emulsion having a low silver chloride content is used, the performance is unstable with respect to the exhaustion of the developing solution, and many black spots are present. .

Example 2 In Example 1, instead of the sensitizing dye 1-5 and the supersensitizer, the above-mentioned sensitizing dyes 2-1 and 2-4 were respectively used in an amount of 2 × 10 ^{-4 with} respect to 1 mol of silver. Samples were prepared in exactly the same manner except that and 1 × 10 ⁻⁴ mol were added, and the same evaluation results as in Example 1 are shown in Table 3.

[0141]

[Table 3]

No. 17 and 18 to 22, No. 23 and 24,
25, Nos. 26 and 27, 28 also show that in this case, the samples containing the dye of the general formula [3] are developers 2, 3, 4
It is understood that the sensitivity difference is small, the occurrence of black spots in the developer 4 is small, and the performance is stable against developer fatigue. Further, as shown in Nos. 29 to 32, when an emulsion containing no iridium or rhodium or an emulsion having a low silver chloride content was used, the performance was unstable with respect to the exhaustion of the developing solution, and black spots also appeared. It is understood that there are many.

Example 3 Sample Nos. 33 to 37 were prepared in the same manner as in Sample No. 2 of Example 1 except that the sensitizing dyes shown in Table 4 were used instead of the sensitizing dyes 1-5. . Further, Sample Nos. 38 to 40 were prepared in exactly the same manner as in Sample No. 18 of Example 2, except that the sensitizing dyes shown in Table 4 were used instead of the sensitizing dyes 2-1 and 2-4. . Table 4 shows the result of evaluation performed in exactly the same manner as in Example 1.

[0144]

[Table 4]

From the comparison with Tables 2 and 3, general formulas 1 and 2
It is understood that good performance can be obtained by using other sensitizing dyes represented by Example 4 A sample was prepared and evaluated in exactly the same manner as the sample 2 of Example 1 except that the compound shown in Table 5 was used as the hydrazine derivative.

[0146]

[Table 5]

From Table 5, it is understood that good performance is exhibited even when other hydrazine derivatives represented by the general formulas [4], [5] and [6] are used.

Example 5 A sample was prepared in exactly the same manner as in Sample No. 2 of Example 1, except that the nucleation accelerators 1 to 4 were added as shown in Table 6, and the same evaluation results were obtained. It shows in Table 6. No. 2
It is understood that the stability is further improved by the addition of the above compound as compared to.

[0149]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03C 1/18 1/295 5/29 501

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contains 1 × 10 ⁻⁸ to 5 per mol of silver.
× 10 ^-6 mol of rhodium compound and 1 per mol of silver
Of chemically sensitized silver halide grains having a silver chloride content of 50 mol% or more containing from 10 to ⁸ × 10 ^-6 mol of an iridium compound, and comprising the emulsion layer or another hydrophilic colloid layer. At least one hydrazine derivative is contained in at least one layer, and the silver halide emulsion is spectrally sensitized with at least one dye selected from the following general formulas [1] and [2] and a dye of the general formula [X]. A silver halide photographic light-sensitive material characterized in that General formula [1] In the formula, Z and Z ₁ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R and R ₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L,
L ₁ and L ₂ each represent a methine group or a substituted methine group. n ₁ and n ₂ each represent 0 or 1. X represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt. General formula [2] [In the formula, Y ₁ and Y ₂ are each a non-metallic atomic group necessary for forming a heterocycle such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R ₁ and R ₂ each represent a lower alkyl group, an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R ₃ represents a methyl group, an ethyl group or a propyl group. X ₁ represents an anion. n ₁ ,
n ₂ represents 1 or 2. m represents 1 or 0,
When it is an intramolecular salt, it represents m = 0. ] General formula [X] Z ₁ and Z ₂ are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, selenazoline nucleus, pyridine nucleus, respectively. , Represents a group of non-metal atoms necessary for completing a benzimidazole nucleus or a quinoline nucleus. R ₁ and R ₂ each represent an alkyl group or an aralkyl group, at least one of which has an acid group. X is a charge balance counterion, m is 0 or 1
Represents 2. A hydrazine derivative is represented by the following general formula [3]:
[4] selected from [5].
The silver halide photographic light-sensitive material described in. General formula [3] In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent, —O— (CH ₂ CH ₂ O) _n — or —O— (CH ₂ CH (OH) CH ₂ O. ) _n - (where n is a group containing a quaternary ammonium cation or as part of a substituent group containing a partial structure of an integer of 3 or more). G ₁ is -CO- group, -COCO- group, -C
S- _{groups, -C (= NG 2 R 2} ) - group, -SO- group, -S
O ₂ - group or _{-P (O) (G 2 R} 2) - represents a group. G
₂ is a mere bond, -O- group, -S- group or -N (R
₂ )-group, R ₂ represents an aliphatic group, an aromatic group, or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group or an arylsulfonyl group. General formula [4] In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G is -CO- group, -SO ₂
A group, a —SO— group, a —COCO— group, a thiocarbonyl group, an iminomethylene group or a —P (O) (R ₃ ) — group, and R ₂ is an electron having at least one carbon atom substituted with G. Represents a substituted alkyl group substituted with an attractive group. R ₃
Represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. General formula [5] In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or an acyl group,
_a represents an aliphatic group, an aromatic group, or a heterocyclic group,
_b represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group. Where R _a and R _b
At least one of them has an adsorption promoting group for silver halide. 3. The silver halide according to claim 2, wherein at least one of the silver halide emulsion layer and the other hydrophilic colloid layer contains at least one amino compound as a nucleation accelerator. Photographic material. 4. An image forming method comprising developing the silver halide photographic light-sensitive material according to claim 1 with a developer having a pH of 9.6 or more and less than 11.0.